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Modulated crystal structures – periodicity in more than three dimensions

Conference Paper · May 2012

DOI: 10.13140/2.1.1058.6403

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Modulated crystal structures – periodicity in more than three dimensions

Modulated crystal structures –

periodicity in more than three dimensions
Andrzej Okuniewski
Department of Inorganic Chemistry, Chemical Faculty, Gdansk University of
Technology, 11/12 Narutowicza Street, 80-233 Gdansk, Poland

Prof. Barbara Becker, Ph.D., D.Sc.

Abstract: The initial definition of a crystal was that it is an object with flat faces. When
diffraction studies were developed it turned out that crystal consists of a highly ordered
particles and it is possible to isolate a small unique part of their structure – a unit cell – and the
definition has been changed to rely on this fact. Nowadays by a crystal we mean any solid
having an essentially discrete diffraction diagram. It is because in recent years scientists found
that there are some solids with discrete diffraction pattern, but there is no possibility to choose
any unit cell. This is the case of quasicrystals discovered by Shechtman (Chemistry Nobel
Prize 2011), polytypes and incommensurately modulated crystals – these all are called
aperiodic crystals. However modulated crystals are not exactly aperiodic – their structures can
be described as periodic, but in more than three (up to six) dimensions…

1. INTRODUCTION 1.1. Periodicity in crystal structures

There are four fundamental states of matter Initially it was believed that a crystal is an
– solid, liquid, gas and plasma. Most object with flat faces. When diffraction
commonly used as a construction material is studies were developed it turned out that
the first one. For example we have crystals consist of a highly ordered particles
buildings, vehicles, furniture, toys and and it is possible to isolate a small unique
electronic devices made of metals, salts, part of their structure – a unit cell.
polymers, semiconductors etc.

Two main classes of solids can be

distinguished: crystalline and amorphous.
Both found wide range of applications, but
the first one is especially interesting.
Crystals may have many unique, highly
predictable and adjustable properties.

Crystal engineering is “the understanding of

intermolecular interactions in the context of
crystal packing and the utilization of such
understanding in the design of new solids Figure 1: Two-dimensional structure with one of
with desired physical and chemical the possible unit cells selected (black
properties” [1]. parallelogram).

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A unit cell is a parallelepiped through the 1.3. Single-crystal X-ray diffraction
translation of which the original structure
will be reproduced (see model in Figure 1). Crystalline solids are characterized by a high
We say therefore that crystals have internal arrangement of particles, so they
translational symmetry. In the ideal can be considered as a three-dimensional
conditions each unit cell should have exactly grid of atoms. A beam of X-rays is scattered
the same arrangement of atoms inside. In when it strikes a crystal. At each point with
fact in real crystals there are some defects high electron density a flat wave is
but their contribution to the statistical diffracted and a spherical wave is formed.
diffraction image is often negligible. Resulting waves interfere and characteristic
diffraction pattern can be observed using
appropriate detector (see model in Figure 2).
1.2. Symmetry and space groups

In addition to the translational symmetry

there can be more symmetry operations
present in a crystal structure: inversion
centers, proper, screw and rotoinversion
axes (2-, 3-, 4- and 6-fold) as well as mirror
and glide planes. There is 230 possible Figure 2: Double-slit (Young) experiment. Flat
combinations of all these operations, which wave is diffracted at A and B, and
are called space groups. They are numbered spherical waves are created. Resulting
in order of increasing symmetry, but also waves interfere and the diffraction
named in a specific way to be easily pattern is formed on the screen (right
side of figure).
recognized by a crystallographer.
Modern (after 1991) definition of a crystal
If there is only translational symmetry in a
relies on this phenomenon [2]:
crystal then it belongs to triclinic P 1 space
group. P stands for ‘primitive’, meaning that
A material is a crystal if it has essentially
this is simple unit cell without centering.
a sharp diffraction pattern.
Usually if a crystal consists of achiral
compounds then there are some centers of
When there is no long-range ordering in a
inversion and it is P 1̄ space group at least.
solid (such as in amorphous materials) then
There are of course space groups with
there is no discrete diffraction pattern.
higher symmetry and more sophisticated
names such as: P 21/c, F ddd, I m3̄m, etc.
Diffraction pattern is an image of so-called
reciprocal lattice (with a unit vectors g)
Why 2-, 3-, 4- and 6-fold axes
related to direct lattice (with a unit vectors
are allowed while 5-fold is not?
a) with the mathematical equation: eiga = 1.
If we consider regular n-sided polygons then
The point group symmetry elements are
only these with n = 3, 4 and 6 can fill the
reflected in a symmetry of a diffraction
plane without gaps. For n = 2 we can think
pattern, while the symmetry elements with
of line segments, which can fill the plane as
the translational components cause some
well. On the other hand points can also fill
characteristic systematic extinctions. If the
the plane without gaps, hence we have the
Friedel law is fulfilled the diffraction pattern
limit groups with ∞-fold axes. It can be
is centrosymmetric regardless of whether the
easily proved that regular n-sided polygons
structure is centrosymmetric or not, hence
with n > 6 cannot fill the plane.
we have only 11 so-called Laue classes.

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Modulated crystal structures – periodicity in more than three dimensions

The exemplary diffraction diagram is are some fixed atomic positions regardless
presented in Figure 3. of temperature then it is static disorder,
when atoms can move feely then it is
dynamic disorder. Sometimes disorders are
somewhat periodic and something
interesting happens to the diffraction image
– additional diffraction spots accompany the
main ones (Figure 4).

Figure 3: Example of diffraction pattern. Source:

Internet Microscope for Schools, The
University of Manchester.
Figure 4: Reconstruction of the diffraction pattern
of some occupationally modulated
structure with satellite diffraction spots
2. MODULATED CRYSTAL visible. Source: V. Petříček, M. Dušek,
STRUCTURES Institute of Physics ASCR, Prague,
Czech Republic.
Over the last years it turned out that there
are crystals, where there is no possibility to
choose a unit cell or it is very big. It is the 2.2. Simple commensurate displacive
case of quasicrystals discovered by Dan modulation in one direction
Shechtman in 1982 [3] (Chemistry Nobel
Prize 2011), polytypes and modulated To illustrate what the modulation is let’s
crystals [4]. This group of solids is called look at the simple example. Imagine that
aperiodic crystals [5]: there is two-dimensional crystal structure
with the square unit cell and two objects
In the following by crystal we mean inside (Figure 5). Position of the gray
any solid having an essentially discrete rectangle is modulated in the a direction.
diffraction diagram, and by aperiodic The modulation function is sinusoidal and
crystal we mean any crystal in which has a period of 6 lengths of the unit cell. If a
three-dimensional lattice periodicity ratio of a modulation period to a unit cell
can be considered to be absent. length is rational then the modulation is
commensurate.
However mentioned systems are not exactly
aperiodic. Structures of the modulated
crystals can be described as periodic, but in
more than three dimensions.

Figure 5: The one-dimensional commensurate

2.1. Disorders and modulations displacive modulation with period of
6 lengths of the unit cell.
Usually if some atoms are found in the one
fraction of unit cells in different positions A real-world example of such a modulation
than in the other we call it disorder. If there type is one of the thiourea polymorphs [6].

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 2.3. Other types of modulations 3. SUMMARY

Except already described displacive The modulated structures often relate to

modulations there are also occupational compounds that are in the interest of
ones. In such case different atoms can be materials sciences, so it is important to
found in the same positions in the understand them and to have tools for their
subsequent unit cells. Both modulation types analysis and description.
can be present in a structure simultaneously,
even one atom can be modulated in both
ways. Furthermore periodic distortions are REFERENCES
sometimes incommensurable with the
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modulations range orientational order and no
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